Vat dyestuffs of the anthraquinone-acridone series and process of making same



Patented Mar. 22, 1932 HEINRECH NERESHEIMER, 0BLUDWIGSEN-QN-THE-RHII'IE, AND ERNST HONOLD, OEIRANORT-ON-THE-MAIN-FECHENHEIM, GERMANY, ASSIGNOBS TO GENERAL INE WQRKS,INC 015 NEW YORK, N. L, A CORPORATIQN OF DELAWARE var nr nernrnson ranANTHR QUINONE-ACEIDONE SERIES AND PROCESS 015 no Drawing. Applicationfiled June a, wee, Serial at. aeonae, and in Germany June 21, was.

In U. LS. Patent 995,936 coloring matters of the anthracene series aredescribed which are obtained by treatin abenzanthronyl-laminoanthraquinone bo y with a condensing agent.

Now we have found that condensation products of these series so far asthey contain a free amino-group and correspond to the m general probableformula:

in which formula one X meansan aminogroup and the other Xs mean hydrogenand the benzanthronyl residue may contain halogen atoms, can beconverted into new valuable vat dyestufis by heating them with anacylating agent,

As acylating agents especially chlorides and anhydrides of aliphatic andaromatic carboxylic acids are suitable. The treatment may be carried outeither by a simple heating of the components or by boiling them in thepresence of "a higher boiling solvent 30 acid binding a ent. Chloridesand anhywh rein one Y means the group NH-acyl and the other Ys meanhydrogen and the benor diluent with or without the addition of anzanthronyl residue may contain halogen atoms. The new products representvat dyestufi's dyeing cotton valuable 'olive shades of a good fastnessto chlorine.

In order to further illustrate our invention the following examples aregiven, the parts being by weight and all temperatures in centigradedegrees; but we wish it to be understood that our invention is notlimited to the examples given, nor to the exact. conditions statedtherein Example 1.46 parts of the condensation product obtainedaccording to U. S. Patent 995,936 by the action of an alcoholic causticpotash so ution on bz 1 benzanthronyl 1 amino-fi-amino-anthra uinone,with about 500'parts o nitrobenzene and 20 parts of benzoylchloride andthe mixture is oiled in an apparatus provided with a stirrer and areflux condenser. After about two hours the mass is cooled down and theseparated dyestufi is filtered ofi and washed out.

It corresponds probably to the formule:

It is soluble in concentrated sulfuric acid with a green colorand dyescotton from a bluish violet vat yellow olive shades of a good fastness.I

' When replacing benzoylchloride by the equivalent amount of cinnamicacid chloride an analogous dyestufi' of very similar properties isobtained.

The condensation may be likewise carried out with the 'addition ofpyridine.

When starting from the condensation prodare mixed ably to the formula:

- 1-amino-5 amino-anthraquinone avery similar dyestufi is obtainedcorresponding prob- E mample 2.46 parts of the same starting material asused in the first paragraph of Example 1 are heated in a nitrobenzenesolution with 30 parts of anthraquinone-Q-carboxylic acid chloride toboiling temperature while stirring for about hours. When cool theseparated dyestufl is isolated and washed out. It corresponds probablyto the formula:

Its solution in concentrated sulfuric acid is greenish colored and thehydrosulfite vat is bluish colored, from which it dyes cotton fastyellow'olive shades.

Example 3.46 parts of the condensation product, used as startingmaterial in Examples 1 and 2, are mixed with about 500 parts ofnitrobenzene and 30 parts of benzoic acid anhydride and the mixture isboiled with stirring in an apparatus provided with a reflux condenser.After about two hours the formed condensation product is filtered ofiand washed out with benzene and alcohol. It is identical with thedyestufl of the first paragraph of Example 1.

The same dyestuif is obtained by heating 46 parts of the startingmaterial with 140 parts of benzoic acid anhydride for about 1 hour atabout 200 and removing the excess of the anhydride by extracting thereaction product with a dilute caustic soda solution.

E wample 4.-46 parts of the starting material of all of the foregoinexamples are suspended with 300 parts 0% acetic acid anhydride and themixture is heated for about 3 hours in an apparatus provided with areflux condenser. The acetylated dyestufl thus formed is filtered offand washed out with glacial acetic acid and water. It corresponds to theprobable formula:

It is soluble in concentrated sulfuric acid with a green color and dyescotton from a violet-blue vat olive shadesof a good fastness to lightand exposure.

E :ra'mple 6.-50 parts of the condensation product obtained by theaction of an alcoholic caustic potash solution onbz-l-benzanthronyl-l-amino- Lamino-anthraquinone are melted with 250parts of benzoic acid anhydride for about 1 hour at about 200. Theformed dyestufi' is isolated as described above. It may be purified byextraction with an organic diluent or a dilute caustic alkali solution.It corresponds probably to the formula:

It dyes cotton from a blue vat olive shades of a particular fastness tolight and exposure.

arts of the condensation The corresponding dyestufi' prepared bytreating the same starting material with acetic acid anhydride dyescotton similar olive shades.

\Ve claim 1. A process for producing new vat dyestuffs which comprisesheating the reaction products of alkaline condensing agents on bz 1benzant-hronyl-l-amino-amino-anthraquinone compounds of the probablegeneral formula:

XtX

wherein one X means an amino-group and the other Xs mean hydrogen andthe benzanthronyl radical may contain a halogen atom in 6-posit'ion,with an acylating agent.

2. As new compounds vat dyestuffs corresponding probably to the generalformula:

wherein one Y means the group NH-acyl and the other Ys mean hydrogen andthe benzanthronyl radical may contain a halogen atom in 6-position,which dyestufi's dye cotton olive shades of a good fastness.

3. As new compounds vat dyestufls corresponding probably to the generalformula:

which dyestuif is soluble in concentrated sulfuric acid with a greencolor and dyes cotton from a bluish violet vat fast yellowish oliveshades.

In testimony whereof, we aflix our signatures.

HEINRICH NERESHEIMER. ERNST HONOLD.

